Supercritical fluid reactions, effect

O. Kajimoto, Solvation in Supercritical Fluids Its Effects on Energy Transfer and Chemical Reactions , Chem. Rev. 1999, 99, 355-389, and references cited therein. 

S. C. Tucker, Solvent density inhomogeneities in supercritical fluids, Chem. Rev., 99 (1999) 391—418 O. Kajimoto, Solvation in supercritical fluids Its effects on energy transfer and chemical reactions, Chem. Rev., 99 (1999) 355-89 S. Nugent and B. M. Ladanyi, The effects of solute-solvent electrostatic interactions on solvatochromic shifts in supercritical C02, J. Chem. Phys., 120 (2004) 874-84 F. Ingrosso and B. M. Ladanyi, Solvation dynamics of C153 in supercritical fluoroform a simulation study based on two-site and five-site models of the solvent, J. Phys. Chem. B, 110 (2006) 10120-29 F. Ingrosso, B. M. Ladanyi, B. Mennucci and G. Scalmani, Solvation of coumarin 153 in supercritical fluoroform, J. Phys. Chem. B, 110 (2006) 4953-62 Y. Kimura and N. Hirota, Effect of solvent density and species on static and dynamic fluorescence Stokes shifts of coumarin 153, J. Chem. Phys., Ill (1999) 5474 ... 

Kajimoto O 1999 Solvation in supercritical fluids its effects on energy transfer and chemical reactions Chem. Rev. 99 355-89... 

For reactions controlled by activation, solvation effects on the reagents and the transition state can affect the equilibrium coefficient for the formation of the transition state and therefore the reaction rate. Equilibria can also be affected by solvation effects on reagents and products. In a supercritical fluid, solvation effects can be controlled by density, and therefore at constant... 

Petsche, I. B. and P. G. Debenedetti 1991, Influence of solute-solvent asymmetry upon the behavior of dilute supercritical mixtures . J. Phys. Chem. 95, 386. Note that very near the critical point, where the local and long-range effects are well separated, it is fundamentally incorrect to ascribe the bulk compressibility, which grows large as a result of long-range fluctuations, on a local scale, that is, to a local volume element. Nevertheless, these models work relatively well. Kajimoto, O. 1999, Solvation in supercritical fluids Its effect on solubility and chemical reactions . Chem. Rev. 99, 355. 

In 1994, we reported the dispersion polymerization of MM A in supercritical C02 [103]. This work represents the first successful dispersion polymerization of a lipophilic monomer in a supercritical fluid continuous phase. In these experiments, we took advantage of the amphiphilic nature of the homopolymer PFOA to effect the polymerization of MMA to high conversions (>90%) and high degrees of polymerization (> 3000) in supercritical C02. These polymerizations were conducted in C02 at 65 °C and 207 bar, and AIBN or a fluorinated derivative of AIBN were employed as the initiators. The results from the AIBN initiated polymerizations are shown in Table 3. The spherical polymer particles which resulted from these dispersion polymerizations were isolated by simply venting the C02 from the reaction mixture. Scanning electron microscopy showed that the product consisted of spheres in the pm size range with a narrow particle size distribution (see Fig. 7). In contrast, reactions which were performed in the absence of PFOA resulted in relatively low conversion and molar masses. Moreover, the polymer which resulted from these precipitation... 

Activity in the area of medium effects (27) has declined greatly in recent years, though there has been some interest in kinetics and mechanisms in supercritical fluids (28). Indeed activation volumes for ring closure reactions of diimine-carbonyls M(CO) (diimine) show some of the most dramatic medium effects. Thus AF values range from +66 to +4 cm3 mol-1 on going from 7% benzene in supercritical C02 (at 35 °C) to 100% benzene (at 25 °C) (29). 

The several theoretical and/or simulation methods developed for modelling the solvation phenomena can be applied to the treatment of solvent effects on chemical reactivity. A variety of systems - ranging from small molecules to very large ones, such as biomolecules [236-238], biological membranes [239] and polymers [240] -and problems - mechanism of organic reactions [25, 79, 223, 241-247], chemical reactions in supercritical fluids [216, 248-250], ultrafast spectroscopy [251-255], electrochemical processes [256, 257], proton transfer [74, 75, 231], electron transfer [76, 77, 104, 258-261], charge transfer reactions and complexes [262-264], molecular and ionic spectra and excited states [24, 265-268], solvent-induced polarizability [221, 269], reaction dynamics [28, 78, 270-276], isomerization [110, 277-279], tautomeric equilibrium [280-282], conformational changes [283], dissociation reactions [199, 200, 227], stability [284] - have been treated by these techniques. Some of these... 

Supercritical fluid (SCF) with the beneficial effects of both liquid- and gas-phase chemistry is an emerging reaction medium for many scientific and technical reasons. The reaction rate and selcectivity are readily tunable by a subtle change in pressure and temperature. 

The scope and limitations of biocatalysis in non-conventional media are described. First, different kinds of non-conventional reaction media, such as organic solvents, supercritical fluids, gaseous media and solvent-free systems, are treated. Second, enzyme preparations suitable for use in these media are described. In several cases the enzyme is present as a solid phase but there are methods to solubilise enzymes in non-conventional media, as well. Third, important reaction parameters for biocatalysis in non-conventional media are discussed. The water content is of large importance in all non-conventional systems. The effects of the reaction medinm on enzyme activity, stabihty and on reaction yield are described. Finally, a few applications are briefly presented. 

In a subsequent study, they used ethylene for a dual purpose, as a substrate as well as a supercritical fluid solvent. This notoriously unreactive olefin to PKR served nicely to give 2-substituted cyclopentenones. Reaction efficiency of each alkyne substrate can be tuned by changing catalyst precursors. Not only Co2(CO)8 but also the two cobalt clusters [Co4(CO)i2] and [Co4(GO)n P(OPh)3 ] work well for some substrates (Equation (8)). The comparison with Rautenstrauch s result clearly shows the beneficial effect of this approach. 

The chlorine atom cage effect was used as a highly sensitive probe for studying the effect of viscosity and the possible role of solvent clusters on cage lifetimes and reactivity for reactions carried out in supercritical fluid solvents. The results of these experiments provide no indication of an enhanced cage effect near the critical point in SC-CO2 solvent. The magnitude of the cage effect observed in SC-CO2 at all pressures examined is well within what is anticipated on the basis of extrapolations from conventional solvents (Fletcher et al., 1998). 

Supercritical solvents can be used to adjust reaction rate constants (k) by as much as two orders of magnitude by small changes in the system pressure. Activation volumes (slopes of In k vs P) as low as —6000 cm3/mol were observed for a homogeneous reaction (97). Pressure effects can also be pronounced on reversible reactions (17). In one example the equilibrium constant was increased from two- to sixfold by increasing the solvent pressure. The choice of supercritical solvent can also dramatically affect an equilibrium constant. An obvious advantage of using supercritical fluid solvents as a media for chemical reactions is the adjustability of the reaction kinetics and equilibria owing to solvent effects. 

In recent years, many efforts are being made to avoid the problematic effects of solvents and many international and national regulations have been established (see Chapter 19 of Ref. [24]) toxic solvents are being replaced by non-toxic ones and environmentally hazardous solvents by harmless ones. The search for new environmentally benign reaction media is the subject of current research and there are many studies into the use of supercritical fluids and room temperature ionic liquids as such media (see 11 and Section 12.7). 

Over the past decade, much progress in supercritical fluid technology has occurred. For example, supercritical fluids have found widespread use in extractions (2-5), chromatography (6-9), chemical reaction processes (10,11), and oil recovery (12). Most recently, they have even been used as a solvent for carrying out enzyme-based reactions (14). Unfortunately, although supercritical fluids are used effectively in a myriad of areas, there is still a lack of a detailed understanding of fundamental processes that govern these peculiar solvents. 

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